AU2004255417A1 - Fungicidal mixtures for controlling fungal pathogens - Google Patents

Description

IN THE MATTER OF an Australian Application corresponding to PCT Application PCT/EP2004/007075 I, Dethard LAMPE Dipl.-Chem., PhD, CChem, MRSC, translator to RWS Group Ltd, of Europa House, Marsham Way, Gerrards Cross, Buckinghamshire, England, -do solemnly and sincerely declare that I am conversant with the English and German languages and am a competent translator thereof, and that to the best of my knowledge and belief the following is a true and correct translation of the PCT Application filed under No. PCT/EP2004/007075. Date: 22 November 2005 D. LAMP For and on behalf of R S Group Ltd I Fungicidal mixtures for controlling rice pathogens The present invention relates to fungicidal mixtures for controlling rice pathogens, comprising, as active components, 5 1) the triazolopyrimidine derivative of the formula 1,

CH

3 F F N N'N F N N Cl and 10 2) fenpropimorph of the formula 1I,

H

3 C CH 3

CH

3 H CCH 0CH3 1- 3 C C1 -, in a synergistically effective amount. Moreover, the invention relates to a method for controlling rice pathogens using 15 mixtures of the compound I with the compound Il and to the use of the compound I with the compound 11 for preparing such mixtures and compositions comprising these mixtures. The compound I, 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tri 20 azolo[1,5-a]pyrimidine, its preparation and its action against harmful fungi are known from the literature (WO 98/46607). The compound II, 4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine, its preparation and its action against harmful fungi are likewise known from the literature 25 (DE 26 56 747, DE 27 52 096; common name: fenpropimorph). Fenpropimorph has been commercially established for a long time, mainly as fungicide for cereals, acting against mildew and rust diseases caused by Ascomycetes or Basidiomycetes. Mixtures of triazolopyrimidine derivatives with fenpropimorph are known in a general 30 manner from EP-A 988 790. The compound I is embraced by the general disclosure of this publication, but not explicitly mentioned. Accordingly, the combination of compound I with fenpropimorph is novel.

2 The synergistic mixtures known from EP-A 988 790 are described as being fungicidally active against various diseases of cereals, fruit and vegetable, for example mildew on wheat and barley or gray mold on apples. 5 Owing to the special cultivation conditions of rice plants, the requirements that a rice fungicide has to meet are considerably different from those that fungicides used in cereal or fruit growing have to meet. There are significant differences in the application method: in addition to the foliar application used in many places, in modern rice 10 cultivation the fungicide is usually applied directly onto the soil during or shortly after sowing. The fungicide is taken up into the plant via the roots and transported in the sap of the plant to the plant parts to be protected. For rice fungicides, high systemic action is therefore essential. In contrast, in cereal or fruit growing, the fungicide is usually applied onto the leaves or the fruits; accordingly, in these crops the systemic action of 15 the active compounds is considerably less important. Moreover, rice pathogens are typically different from those in cereals or fruit. Pyricularia oryzae and Corticium sasakii (syn. Rhizoctonia solani) are the pathogens of the diseases most prevalent in rice plants. Rhizoctonia solani is the only pathogen of 20 agricultural significance from the sub-class Agaricomycetidae. In contrast to most other fungi, this fungus attacks the plant not via spores but via a mycelium infection. For this reason, findings concerning the fungicidal activity in the cultivation of cereals or fruit cannot be transferred to rice crops. 25 Practical agricultural experience has shown that the repeated and exclusive application of an individual active compound in the control of harmful fungi may lead in many cases to a rapid selection of such fungus strains which have developed natural or adapted resistance against the active compound in question. Effective control of these 30 fungi with the active compound in question is then no longer possible. To reduce the risk of selection of resistant fungus strains, mixtures of different active compounds are nowadays usually employed for controlling harmful fungi. By combining active compounds having different mechanisms of action, it is possible to ensure a 35 successful control over a relatively long period of time. It was an object of the present invention to provide, with a view to effective resistance management and an effective control of rice pathogens at application rates which are as low as possible, mixtures which, at a total amount of active compounds applied 40 which is reduced, have an improved effect against the harmful fungi.

3 We have found that this object is achieved by the mixtures defined at the outset. Moreover, we have found that simultaneous, that is joint or separate, application of the compound I and the compound II or successive application of the compound I and the 5 compound 11 allows better control of rice pathogens than is possible with the individual compounds. When preparing the mixtures, it is preferred to employ the pure active compounds I and II, to which further active compounds Ill and IV against harmful fungi or other pests, 10 such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers can be added as required. Further suitable active compounds in the above sense are, in particular, fungicides selected from the following group: 15 * acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl, * amine derivatives, such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine or tridemorph, * antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin 20 or streptomycin, * azoles, such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, simeconazole, tebuconazole, 25 tetraconazole, triadimefon, triadimenol, triflumizole or triticonazole, * dicarboximides, such as iprodione, myclozolin, procymidone or vinclozolin, * dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram or zineb, * heterocyclic compounds, such as anilazine, boscalid, carbendazim, carboxin, 30 oxycarboxin, cyazofamid, dazomet, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, picobenzamid, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole or triforine, 35 9 copper fungicides, such as Bordeaux mixture, copper acetate, copper oxychloride, basic copper sulfate, * nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton or nitrophthal isopropyl, 4 * phenylpyrroles, such as fenpiclonil or fludioxonil, e sulfur, * other fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezine, diclocymet, diethofencarb, 5 edifenphos, ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, phosphorous acid, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, tolclofos methyl, quintozene or zoxamide, * strobilurins, such as fluoxastrobin, metominostrobin, orysastrobin, picoxystrobin, 10 pyraclostrobin or trifloxystrobin, * sulfenic acid derivatives, such as captafol, captan, dichlofluanid, folpet or tolylfluanid, * cinnamides and analogous compounds, such as flumetover. 15 In one embodiment of the mixtures according to the invention, the compounds I and I1 are admixed with a further fungicide IlIl or two fungicides Ill and IV. Suitable components IlIl and IV are in particular the following fungicides: 20 Amine derivatives, such as dodine, dodemorph, fenpropimorph, fenpropidin, imoctadine, spiroxamine or tridemorph; azoles, such as bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, 25 prothioconazole, simeconazole, tebuconazole, tetraconazole, triflumizole or triticonazole; heterocyclic compounds, such as boscalid, carbendazim, carboxin, cyazofamid, fenarimol, flutolanil, picobenzamid, proquinazid, pyrifenox, quinoxyfen or thiophanate methyl; 30 dithiocarbamates, such as maneb, mancozeb, metiram or thiram; and strobilurins, such as fluoxastrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, other fungicides, such as benthiavalicarb, chlorothalonil, cyflufenamid, diclofluanid, fenhexamid, fluazinam, fosetyl, fosetyl-aluminum, phosphorous acid, iprovalicarb, 35 metrafenone and pencycuron. Mixtures of the compounds I and Il with a component Ill are preferred. Mixtures of the compounds I and II are particularly preferred.

5 The mixtures of compounds I and II, or the compound I and the compound 11 used simultaneously, that is jointly or separately, exhibit outstanding action against rice pathogens from the classes of the Ascomycetes, Deuteromycetes and Basidiomycetes. They can be used for the treatment of seed and as foliar- and soil-acting fungicides. 5 The compounds I and Il are preferably applied by spraying the leaves. They are especially important for controlling harmful fungi on rice plants and their seeds, such as Bipolaris and Drechslera species, and also Pyricularia oryzae. They are particularly suitable for controlling sheath blight on rice, caused by Corticium sasakii 10 (syn. Rhizoctonia solani). Moreover, the inventive combination of compounds I and Il are also suitable for controlling other pathogens, such as Septoria and Puccinia species in cereals such as wheat or barley and Altemaria and Botrytis species in vegetables, fruit and grapevines. 15 The compound I and the compound 11 can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures. 20 The compound I and the compound I are usually applied in a weight ratio of from 100:1 to 1:100, preferably from 20:1 to 1:50, in particular from 10:1 to 1:10. The components Ill and IV are added if required in a ratio of from 20:1 to 1:20 with respect to compound I. 25 Depending on the type of compound and on the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha. 30 Correspondingly, the application rates of the compound I are generally from 1 to 1000 g/ha, preferably from 10 to 750 g/ha, in particular from 20 to 500 g/ha. Correspondingly, the application rates of the compound 11 are generally from 1 to 1000 g/ha, preferably from 10 to 750 g/ha, in particular from 20 to 500 g/ha. 35 In the treatment of seed, the application rates of the mixture are generally from 0.001 to 1 g/kg of seed, preferably from 0.01 to 0.5 g/kg, in particular from 0.01 to 0.1 g/kg. In the control of harmful fungi pathogenic to rice plants, the separate or joint application 40 of the compounds I and II or of the mixtures of the compounds I and 11 is carried out by 6 spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants. The compounds are preferably applied jointly or separately by applying granules or by dusting the soils. 5 The mixtures according to the invention or the compounds I and Il can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the particular purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention. 10 The formulations are prepared in a known manner, for example by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants. Solvents/auxiliaries which are suitable are essentially: - water, aromatic solvents (for example Solvesso products, xylene), paraffins (for 15 example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used. 20 - carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose. 25 Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore 30 condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty 35 alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

7 Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, 5 paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water. Powders, materials for spreading and dustable products can be prepared by mixing or 10 concomitantly grinding the active substances with a solid carrier. Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, 15 limestone, lime, chalk, bole, less, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers. 20 In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compounds. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum). 25 The following are examples of formulations: 1. Products for dilution with water A) Water-soluble concentrates (SL) 10 parts by weight of the active compounds are dissolved in water or in a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound 30 dissolves upon dilution with water. B) Dispersible concentrates (DC) 20 parts by weight of the active compounds are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a 35 dispersion. C) Emulsifiable concentrates (EC) 8 15 parts by weight of the active compounds are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). Dilution with water gives an emulsion. 5 D) Emulsions (EW, EO) 40 parts by weight of the active compounds are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). This mixture is introduced into water by means of an emulsifier (Ultraturax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. 10 E) Suspensions (SC, OD) In an agitated ball mill, 20 parts by weight of the active compounds are comminuted with addition of dispersant, wetters and water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active 15 compound. F) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of the active compounds are ground finely with addition of dispersants and wetters and made into water-dispersible or water-soluble granules by 20 means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. G) Water-dispersible powders and water-soluble powders (WP, SP) 75 parts by weight of the active compounds are ground in a rotor-stator mill with 25 addition of dispersant, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound. 2. Products to be applied undiluted 30 H) Dustable powders (DP) 5 parts by weight of the active compounds are ground finely and mixed intimately with 95% of finely divided kaolin. This gives a dustable product. 1) Granules (GR, FG, GG, MG) 35 0.5 part by weight of the active compounds is ground finely and associated with 95.5% carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted. J) ULV solutions (UL) 9 10 parts by weight of the active compounds are dissolved in an organic solvent, for example xylene. This gives a product to be applied undiluted. The active compounds can be used as such, in the form of their formulations or the use 5 forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of 10 the active compounds according to the invention. Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can 15 be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water. 20 The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%. The active compounds may also be used successfully in the ultra-low-volume process 25 (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives. Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate just immediately 30 prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1. The compounds I and Il or the mixtures or the corresponding formulations are applied by treating the harmful fungi or the plants, seeds, soils, areas, materials or spaces to 35 be kept free from them with a fungicidally effective amount of the mixture or, in the case of separate application, of the compounds I and 1l. Application can be carried out before or after infection by the harmful fungi.

10 The fungicidal action of the compound and the mixtures can be demonstrated by the experiments below: The active compounds, separately or jointly, were prepared as a stock solution with 5 0.25% by weight of active compound in acetone or DMSO. 1% by weight of the emulsifier Uniperol@ EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution, and the solution was diluted with water to the desired concentration. 10 Use example - Activity against sheath blight on rice caused by Corticium sasakii (syn. Rhizoctonia solan) Pots of rice plants of the cultivar ,,Tai-Nong 67" were sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. The 15 next day, oat grains infected with Corticium sasakii were placed into the pots (in each case 5 grains per pot). The plants were then placed in a chamber at 26*C and maximum atmospheric humidity. After 11 days, the sheath blight on the untreated but infected control plants had developed to such an extent that the infection could be determined visually in %. 20 Evaluation is carried out by determining the infected plants in percent. These percentages were converted into efficacies. The efficacy (E) is calculated as follows using Abbot's formula: 25 E = (1 - a/p) -100 a corresponds to the fungicidal infection of the treated plants in % and 30 p corresponds to the fungicidal infection of the untreated (control) plants in % An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants are not infected. 35 The expected efficacies of the mixtures of active compounds are determined using Colby's formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacies. 40 Colby's formula: 11 E = x + y - x-y/100 E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b 5 x efficacy, expressed in % of the untreated control, when using active compound A at the concentration a y efficacy, expressed in % of the untreated control, when using active compound B 10 at the concentration b The comparative active compounds used were Compounds A and B known from the fenpropimorph mixtures described in EP-A 988 790:

CH

3

CF

3 F F F H 3 C NH N A B N'N F Cl N N CI N N Cl 15 Table A - Individual active compounds Concentration of active Efficacy in % of the Example Active compound compound in the spray untreated control liquor [ppm] 1 control (untreated) - (90% infection) 2 I 4 67 1 33 4 0 3 II (fenpropimorph) 0 1 0 4 Comparative 4 0 ._ compound A 1 0 5 Comparative 4 72 compound B 1 0 Table B - Mixtures according to the invention Mixture of active compounds; Example Observed efficacy Calculated efficacy*) concentration; mixing ratio 12 Mixture of active compounds; Example cntratiomin Observed efficacy Calculated efficacy*) concentration; mixing ratio I + 11 6 1+4ppm 100 33 1:4 I + 11 7 4+1 ppm 100 67 4:1 *) efficacy calculated using Colby's formula Table C - Comparative tests mixtures known from EP-A 988 780 Mixture of active compounds; Example Observed efficacy Calculated efficacy*) concentration; mixing ratio A+l1 8 1 +4ppm 0 0 1:4 A+ll 9 4+1ppm 0 0 4:1 B + 11 10 1+4ppm 0 0 1:4 B + 11 11 4+1 ppm 67 72 4:1 *) efficacy calculated using Colby's formula 5 The test results show that the mixtures according to the invention are, owing to strong synergism, considerably more effective against sheath blight than the fenpropimorph mixtures known from EP-A 988 780, although comparative compound B, as individual active compound, has an activity comparable to that of compound I.

Claims (10)

1. A fungicidal mixture, comprising 5 1) the triazolopyrimidine derivative of the formula 1, CH 3 F F N N F N N CI and 2) fenpropimorph of the formula 11, CH CH H 3 C 3 H H CH 3 0 II 10 3 in a synergistically effective amount.

2. A fungicidal mixture, comprising the compound of the formula I and the compound of the formula II in a weight ratio of from 100:1 to 1:100. 15

3. A fungicidal composition, comprising a liquid or solid carrier and a mixture as claimed in claim 1 or 2.

4. A method for controlling harmful fungi which are rice pathogens, which comprises 20 treating the fungi, their habitat or the plants, the soil or the seeds to be protected against fungal attack with an effective amount of the compound I and the compound 11 as set forth in claim 1 or of the composition as claimed in claim 3.

5. A method as claimed in claim 4, wherein the compounds I and 11 as set forth in 25 claim 1 are applied simultaneously, that is jointly or separately, or in succession.

6. A method as claimed in claim 4, wherein the mixture as claimed in claim 1 or 2 or the composition as claimed in claim 3 is applied in an amount of from 5 g/ha to 2000 g/ha. 30 14

7. A method as claimed in claim 4 or 5, wherein the mixture as claimed in claim 1 or 2 or the composition as claimed in claim 3 is applied in an amount of from 0.001 to 1 g/kg of seed. 5

8. A method as claimed in any of claims 4 to 7, wherein the harmful fungus Corticium sasakii is controlled.

9. Seed, comprising the mixture as claimed in claim 1 or 2 in an amount of from 0.001 to 1 g/kg. 10

10. The use of the compound I and the compound Il as set forth in claim 1 for preparing a composition suitable for controlling harmful fungi.